Cement composition and method of making the same



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comma R PLASTlG Patented Oct. 17, 1944 Examin UNITED STATES PATENT OFFICE CEMENT COMPOSITION AND METHOD OF MAKING THE SAME Edward W. Scripture, Jr., Shaker Heights, Ohio No Drawing. Application August 14, 1941, Serial No. 406,905

6 Claims.

tion for ri'gd ng agents It particularly relates to a me od-of grinding cements wherein the MT increased with existing equipment.-

Hydraulic cements are manufactured by mixing together in a finely divided state, in suitable proportions, either by a wet process or a dry process, suitable raw materials, usually of a calcareous and a silicious nature, to produce after the manufacturing operation chemical compounds having hydraulic and cementitious properties in the desired proportions. The mixed raw materials are heated together in a kiln, in modern practice usually a rotary kiln, and burned at a temperature which causes sintering, or in some cases they may be burned to actual fusion. After burning, the resultant product, usually called clinker, is allowed to cool. In this state of manufacture the cementitious compounds have been formed but exist in a physical state, that of relatively large pieces with very low surface area, in which they cannot be used to make mortar or concrete mixes. This cement clinker is then reduced by grinding, usually in a ball mill of either the intermittent or continuous type, to a relatively fine state of subdivision having a relatively large surface area. During this stage, calcium sulphate in one form or another is usually added to the cement to prevent too rapid set.

The hydraulic properties of the cement depend on its chemical composition and on the burning operation, but also to a considerable extent on the grinding and the degree of fineness to which it has been reduced. For example, the plastic properties and the rate at which the cement hydrates are markedly affected by the surface area, that is, the degree of grinding.

The grinding of cement clinker requires the use of considerable equipment and consumes a substantial period of time. In order to operate the equipment, power in one form or another is required. The grinding operation, therefore, adds substantially to the cost 01' manufacture of cement and it will be obvious that the finer the grinding the greater will be this cost.

It has heretofore been known that certain materials when added to cement clinker in the mill will facilitate grinding and will increase the efficiency of this operation. In order to be useful, such materials must not have an adverse effect on the plastic or hydraulic properties of the ce- 10 wherein the cost ofgrinding the cement clinker.

ment, as by retarding or preventing hydration. It is preferable that such materials, which may be termed "grinding aids, shall improve the properties of the cement and of the mortar or concrete in which they are used with respect to strength, rate of hardening, plasticity, durability, or other properties.

It is an object of this invention to provide a method of producing finely ground cement,

is reduced.

It is a further object of this invention. to provide a method for grinding cements, wherein the time required to reduce cement clinker to a given surface area is reduced.

It is a further object of this invention to provide a method wherein the finer grinding of cement clinker and the production of a cement of greater surface area are facilitated.

It is a further object of this invention to provide a ground cement clinker which shall have improved plastic and hydraulic properties.

In my copending application Serial No. 406,904 of even date herewith, I disclosed that these ob- J'ects are accomplished by incorporating with the cement clinker in the grinding mill a relatively small percentage, based on the weight, of a compound having the general formula: W

COOR

"swan-an "a Cal i4 n accor ai'ice W1 the present invention, it

has been found that a further improvement in grinding time and a further improvement in the properties of the cement are obtained by incorporating in the grinding mill with the cement clinker both a small amount of a suitable we tin agent and a small amount of one or more com oundsof the above eneral formula. While eac of these ingredients is efiective in lowering the grinding time and improving the properties of structures produced from mixes containing the ground cement, both ingredients coact to produce a greater improvement than that ob'-.

tainable with an equal total quantity of either ingredients.

The as used herein, include wgttjgg agents, only tha well-recognized class of reagents capable of markedly lowering the surface tension pound havl ng the general formula RCHzX where n or more R is an aliphatic chain preferably carbon a oms and X is a %onate or s a e Th ormulae group. e igepons, having e f orn-o-oon cm-Nnoon Hr-S 01M Hr-S OtM where R is an aliphatic group and M is an alkali metal as well as the olyglycerol esters, are' also particularly desirable for use in the present invention with the substituted benzoic acids or their derivatives. The salic Iates and salic lic acid 'are the preferred compoun s for use in comBmation with one or more of the above described wetting agents as an addition to the cement clinker. Examples of these very effective compounds are:

(a) The metal salicylates including salicylates of the alka me a s, the alkaline ear me a s, mercw, M5111 and othersl" Examples of other compounds which contain the salicylate grouping and which are effective are:

(b) Salic lic acid, acet lsalic lic acid, sulphosalicylic 8.01% and cafieine-salicylic acid.

Other very effective compounds are he subf stituted benggig gels}; and derivatives thereof. Examp es of these are:

in the benzene nucleus without harming the effectiveness of the compounds. Thus, sulphosalicylic acid. which is a sulfonated salicylic acid, is

ave'ry efiective mater a It has been observed that in the grinding of cement clinker the balls in the ball mill, and the walls of the mill tend to become coated with the more or less finely ground cement. This formation on the grinding surfaces apparently exerts a cushioning efiect, such that the rate of grinding is thereby greatly diminished.

I have found that when small amounts of one or more suitable wetting agents, together with one or more of the compounds of the above general formula, are added to cement clinker in a ball mill, the formation of a cushion on the grinding surfaces appears to be reduced and the efliciency of the grinding operation is increased. In this manner the time required, and consequently the power input, to grind to a particular degree of fineness or surface area is reduced, or for a given time and power input the degree of fineness or surface area is increased. The saving in grinding time depends to a larger extent both on the quantity of the above described compounds, which are present in cement, and on the degree of fineness desired in the cement. With an increase of the salicylic acid or equivalent material from effective amounts, such as .005%, there is an increased efliciency in grinding until about .05% or .1% on the weight of the cement is present. Although as much as .5% of salicylic acid or equivalent compound of the above general formula may be incorporated with the cement clinker, appreciable further improvement in results is not obtained. When the cement is ground to a greater surface area, the reduction in the time required to reach this surface area by means of the present invention is substantially increased.

Lauryl alcohol sodium sulfate is an especially desirable sur ace ac ive compound and like other wetting agents it should be present in amounts less than .5%, and preferably less than .3% of the weight of the cement; more than .5% adversely affects the strength of the cement. As little as .001% or .01% on the weight of the cement of a wetting agent in combination with the salicylate compound, or substituted benzoic acids or derivatives thereof having the above general formula, produces noticeable improvements in grinding efiiciency and in the strength of a suitable hardened cement mix. The total amount of the salicylate compound and of the active wetting agent present should preferably be less than .5% of the weight of the cement. The utilization of both a wetting agent and a compound of the above general formula is also advantageous in that a larger total quantity of grinding aid may be present in the cement, and maximum decrease in grinding time may be had with substantially maximum improvement in the strength of the mixes containing the cement thus produced.

The following examples illustrate the present invention:

Example 1 ,sq. cm./gram, that of the cement ground with this addition was 1940 sq. cm./gram. With smaller proportions of salicylic acid, similar results were secured; but, the increases in surface area were somewhat less. With larger proportions of salicylic acid, similar results were also secured; but, in this case the increases in surface area secured were slightly greater.

The improvement in grinding eificiency is not the entire benefit to be derived from the use of a composition which comprises both a compound of the type of salicylic acid and a compound of the type of sodium lauryl sulfate. Such a composition also imparts desirable characteristics to the concrete or mortar made from such cements. In the first place, the amount of water required to produce a given consistency or workability in a given concrete mix is substantially reduced. Second, the compressive strengths secured at any age are increased. Third, the unit weight of a given concrete mix is reduced, which indicates that a greater than normal proportion of air is incorporated in the mix in the form of closed voids and it is considered that this will increase durability. Fourth, the tendency of the concrete to )6. COMPOSITIONS,

COATING OR PLASTIC bleed, that is, for the water to separate from the cement, is reduced.

Example 2 To illustrate the effects of this composition on the properties of concrete, tests were made according to standard procedure. Concrete mixes in the proportions of 5147 lbs, cement, 1340 lbs. sand and 1985 lbs. inch stone were made up with sufficient water to give approximately equal consistencies in all mixes. Cylindrical specimens, 6 inches by 12 inches, were prepared and determinations made of the weight per cubic foot and compressive strengths at various ages. The results of two such series of tests on concrete ground to the same surface area, with and with- Examiner small amount of salicylic acid or other compound of similar constitution, as above set forth.

It will be seen from the above tha'fi' an outstanding improvement in the strength of the cement is obtained by the practice of the present invention. By grinding one or more of the above described compounds with the cement, they are more uniformly dispersed in the cement and are forced into intimate contact and even into the pores of the individual particles of cement, so that in most instances superior results are ob tained.

It will be apparent that the compound which facilitates grinding, such as salicylic acid or a. compound of similar constitution, may be added out the compositions above described, were as to the cement clinker as a dry powder o in sofollows: lutiog gr in another physicaffo'rm. t illafiti Compressive strength, Surface water Unit lbs/sq. in.

area, 815 lsak Slump, in. weight, sq. cmJg. E L, lbsJcu. it.

{1 day Bdays 7days 28days 1 Cement ground without addition While in the example which I have given I have used .05% salicylic acid on the weight of the cement and .01% sodium lauryl sulfate, other proportions may equally well be used, depending on the results desired. With a smaller proportion of salicylic acid or compound of the same type, the improved grinding efficiency will be less and with larger portions slightly greater. Grinding is also improved by the use of larger proportions of sodium lauryl sulfate or similar compound. For example, with 005% sodium lauryl sulfate and .O5% salicylic acid, a reduction of grinding time of about 42% was found for a surface area of 2110 sq. cm./gram, while with .01% sodium lauryl sulfate and .05% salicylic acid, the reduction was about 43%. Also, the greater proportion of sodium lauryl sulfate permitted a greater reduction in water for a given consistency and produced a larger decrease in unit weight.

Whereas, I have found that if sodium lauryl sulfate, or similar fatty acid sulfate, is added to the cement after grinding in considerable proportions substantially in excess of .01% of the weight of the cement, the strength of the concrete is more or less seriously impaired, I find that when such materials are added before grinding or ground with the clinker, these deleterious effects are not observed.

I have found that the desirable effects described may be secured by the addition of sodium lauryl sulfate, or other fatty acid sulfate, or of compounds which have a similar efiect in reducing surface tension such as Vinsol resin and other compounds of the class abmd. These compounds may be used alone, but to secure the most beneficial effects on both the grinding of the cement clinker and on the properties of the concrete or mortar made from such cements, they are preferably used in combination with a be apparent that more or less than the usual amount of gypsum or other form of calcium sulfate may be added, depending on the desired characteristics of the cement, and that other substances may be added to the cement at the same time or subsequently.

What I claim is:

1. In a process of grinding cement the steps which comprise adding to the cement clinker a small amount of a wetting agent capable of lowering the surface tension of neutral and alkaline aqueous solutions and of a member of the group consisting of substituted benzoic acids, salts and esters thereof, and grinding the clinker.

45 2. A process of grinding cement which consists in adding to the cement clinker a small amount of a fatty alcohol alkali metal sulfate and a small amount of a member of the group consisting of a substituted benzoic acid, salts and esters thereof,

and grinding the clinker.

3. A process of grinding cement which consists in adding to the cement clinker a fatty alcohol alkali metal sulfate and a small amount of salicylic acid, and grinding the slinker.

4. As a new composition of matter, a dry cement ground with a small amount of lauryl alcohol alkali metal sulfate and of salicylic acid.

5. As a new composition of matter, a dry cement ground with a small amount of a fatty alcohol alkali metal sulfate and of a substituted ble of lowering the surface tension of neutral and alkaline aqueous solutions and a mono-substituted benzoic acid, and thereafter grinding the clinker.

EDWARD W. SCRIPTURE, J11. 

